CO2 chemistry has drawn considerable attention as abundant, low cost, and renewable carbon source in the past decades. The natural stability of CO2 made its utilization a daunting challenge under mild conditions. Recently, there has been significant progress of CO2 fixation by using cheap and abundant functionalized polyoxometalate (POM) catalysts. In this review, the POM catalytic system for transformation of CO2 into valuable compounds such as urea, cyclic carbonate, quinazoline-2,4(1H,3H)-diones, α-methylene cyclic carbonate, oxazolidinones etc. were discussed. The future of POM catalysis for sustainable chemistry lies in the synthesis of highly functionalized task-specific POM catalysts, and rational design of novel reactions which would eventually pave the pathway for the establishment of green, effective, inexpensive and sustainable technologies.